Table 7-1 Common Reactions of Organotransition Metal Complexes
Schematic example
Reaction type
∆ Coordination
number of M
∆ e−
count
Text
section
0
0
0
7-1
Ligand
substitution
L'' + LnML'
LnML'' + L'
Oxidative
addition
LnM + X-Y
LnM(X)(Y)
+2
+2
+2
7-2
Reductive
elimination
LnM(X)(Y)
LnM + X−Y
−2
−2
−2
7-3
0
−1
−2
8-1-1
0
−1
−2
8-1-1
0c
0
0
8-2
0
0
0
8-3
0
0
0
8-4
0
0
0
8-4
Y
1,1-Insertion
a
1,2-Insertion
a
Z
LnM X
Y
LnM
Y
LnM X Y
Z
1
1
X1
LnM X Z
Z2
X
1
Nucleophilic
additionb
LnM
Nucleophilic
abstractionb
LnM CR + Nuc−H
Electrophilic
additionb
LnM−X=Z + E+
Electrophilic
abstractionb
LnM−X−Z−Y + E+
R
π- and σ-Bond
metathesisd
C
C
R'
a
∆ Oxidation
state of M
+ Nuc:−
Y
2
[LnM−X−Z−Nuc]−
Z
O
O
LnM−H + Nuc
[LnM=X−Z−E]+
LnM+
X
Z
+ E-Y
CR
R
+
C
C
or
X
Y
+
W
Z
R C C R
X W
or
+
+
Y Z
R' C C R'
11-1 and 11-4
R'
The reverse reaction, called deinsertion or elimination, is also possible.
There is no one general reaction; several variations are possible.
cDepends upon change in hapticity; e.g., X=Z going from η3 to η2 results in a 2 e− reduction.
d∆ oxidation state, coordination number, and e− count are not applicable here, especially in π-bond metathesis where the metal complex is a catalyst.
b